Brightening of fine fabrics



United States Patent BRIGHI ENING OF FINE FABRICS Louis E. Craig, Pryor, 0kla., assignor to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed June 21, 1956, Ser. No. 592,721

7 Claims. (Cl. 1'17--33.5)

colors of the dyed textile products. It is an important object of this invention to provide an improved process for treating textile materials to whiten and brighten the same.

Another object of this invention is the provision of an improved process for brightening textile materials by treat- 7' ing the same with an aqueous dispersion of a diphenylindole.

A further object of this invention is the provision of novel brightening agents comprising substituted diphenylindoles.

Other objects of this invention will appear from the following detailed description and claims.

In accordance with this invention, the brightening of textile fibers, filaments and fabrics of synthetic materials is efiected by applying to said fibers, filaments and fabrics compounds consisting of diphenylindoles and of variously substituted diphenylindoles such as, for example, 2,3-diphenylindoles which are represented by the. following formula:

where R may be hydrogen, alkyl, aryl, arylalkyl, alicyclic, or an alkyl group containing atoms other than carbon, such as oxygen, nitrogen, and the'like, as exemplified by B-hydroxyethyl, p-aminoethyl, B-cyanoethyl, etc., and R and R may be hydrogen, alkyl, aryl, arylalkyl, or anynon-chromo'phoric group such-as hydroxyl, alkoxyl, amino,

"ice

2 alkylamino, acylamido, carboalkoxyl, cyano, and the like. R and R may also be halogen. More than one R may be present on the benzenoid ring of the indole nucleus.

-Related compounds which are also useful for brightening textile materials can be represented by the following formulas:

1 l N R1 I where R and R are defined as above and X is -CH 3 O-, S-, SO -CO, a diphenyl linkage, and the like. 7

The aforementioned compounds are suitable in some cases for use in brightening textile materials of nylon, cellulose esters, a polyester of terephthalic acid and ethylene glycol, a polymer of acrylonitrile, a copolymer of acrylonitrile and vinyl chloride.

Preferably, the brightening agents of this invention are applied to the textile materials from an aqueous dispersion. Thus, the diphenylindole to be used is dissolved in a suitable water-miscible organic solvent such as, for example, ethyl alcohol, acetone, dimethylformamide, dioxane, or a mixture of two of said solvents, and a small amount of the solution is added to water whereby a milky dispersion is obtained. The textile materials are treated with this dispersion. It has been found that the presence of soap or a synthetic surface active agent in said dispersion is beneficial. Satisfactory brightening of textile materials may also be obtained by washing the same, employing ordinary washing operations, with a soap or a synthetic detergent in which the diphenylindoles are incorporated. Also these compounds may be applied in the form of the amine acid salt.

The diphenylindoles employed in accordance with the instant invention may be prepared from the appropriate phenylhydrazine and the appropriate a-phenylacetophenone by the Fischer indole synthesis, as follows:

i it NNHi c on cidic phenylhydrazone catalysts The phenylhydrazines might be chosen from the following: p-arnino-, m-amino-, p-acetamido-, m-acetamido-, pfor-rnarnido-, m-formamido-, p-chloro-, rn-chloro-, pbrom-, m-bromo-, 2,4-dichloro-, 2,4-dibromo-, p-phenyl-, o-phenyl-, p-methoxy-, o-methoxy-, p-ethoxy-, p-hydroxy-, m-hydroxy-, o-methyl-, m-methy1-, p-methyl-, 2,5-dimethy1-, 2,3 dimethyl-, 2,5 dimethoxy-, 4 acetamido-Z- methyl-, p-carbethoxy-, and the like. ozand fi-naphthylhydrazines and substituted naphthylhydrazines such as 4-bromo-, 4-chloro-, 5-methoxy-, 5-acetamino-, and 8-acetamido oz naphthylhydrazine and 3 bromo-, 3- chloro-, 5-rnethoxy-, 6-methoxy-, 3-acetamido-, 6-acetamidoand 7-acetamido-fi-naphthylhydrazine can also be used. The dihydrazines prepared by diazotization and reduction of 4,4'-biphenyldiamine (benzidine), 2,4'-biphenyldiann'ne, di(p-aminophenyl) methane, and di(0- aminophenyl)methane may also be used.

The u-phenylacetophenones may be selected from the following substituted acetophenones: u- (p-aminophenyl)-, p-amino-u- (p-aminophenyl) a- (m-aminophenyl) a- (p- 4 acetamidophenyl)-, a-(p-methoxyphenyl)-, a-4-biphenylyl-, p-bromo-u-(p-bromophenyl)-, o-bromo-a-phenyl, pchloro-a-phenyl, u-(o-chlorophenyl)-, 2,4-dihydroxy-aphenyl-, a-(2,4-dimethoxyphenyl)-, a-(2,3-dimethoxyphenyl) -2,3-dim ethoxy-, 3-hydroxy-a- (p-hydroxyphenyl) p-methoxy-a-phenyL, u-(m-methoxyphenyl)-, and a-(pmethoxyphenyl) acetophenone.

Alternatively, the diphenylindoles may be prepared by condensation of the appropriate aromatic amine with the appropriate benzoin, as follows:

OH O a ll NHR H O Acidic R +R catalyst Some of the amines which may be used as o-, m-, and ptoluidine; o-, m-, and p-anisidine; mand p-chloro and bromo anilines; mand p-aminoacetanilides; 2- and 4- biphenylamine; N-methyl-, N-ethyl, N- (B-hydroxyethyl)-, and N-benzyl-anilines; N-methyl-, 0-, mand p-toluidines; the xylidines; 2,5-dimethoxyaniline; o-, mand p-aminophenol; mand p-amino-N-methylacetanilides; aand ,3- naphthylamine; 3-chloro-, 5-methoxy-, 4-acetamido-, 5- acetamidoand 8-acetamido-a-naphthylamine; 3-bromo-, 3-chloro-, 3-acetamido-, 6-acetamido-, 3-hydroxy-, and 6- hydroxy-fl-naphthylamine. The bis-2,3-diphenylindoles can be prepared from 4,4-biphenyldiamine, 2,4'-biphenyldiamine, di(p-aminophenyl)methane, di(o-arninophenyl)methane, 4,4-diaminodiphenyl ether, 4,4'-dian1inodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, and the like.

Benzoin or substituted benzoins such as 4-methoxy-, 3,4-methylene-dioxy-, 4-dimethylamino-, 2-hydroxy-, 2- hydroxy-, 4-methoxy-, 2,2'-dimethoxy-, 4,4-dimethoxy-, 4,4 -diacetamino-, 3,3,4,4',5,5'-hexamethoxy, 4,4'-diphenyl, 4-phenyl-, 4-chloro-, 4'-chloro-, 4,4'-dichloro-, 3,3-dichloro-, 4-chloro-4'-methoxy-, 4,4'-diaminobenzoin, andthe like, may be used.

Groups may also be introduced into the parent 2,3- diphenylindole by substitution reactions; for example, the hydrogen on the nitrogen of the indole ring can be replaced by alkyl groups by alkylation, as for example, with alkyl halides (e.g., methyl iodide, ethyl iodide),

.alkyl sulfates (dimethyl and diethylsulfate). The 18- cyanoethyl group may be introduced by cyanoethylation with acrylonitrile in the usual manner. Nitration followed by reduction gives the amino-substituted 2,3-diphenylindole which may be converted to acyl derivatives.

The amount of the 2,3-diphenylindole employed in treating the textile material is from 0.05 to 0.5%, based on the Weight of the textile material.

Appreciable brightening of the colors is also observed when the compounds employed in the instant invention are incorporated in films and plastic bodies having a basis of the synthetic materials of the fibers, filaments and fabrics above mentioned.

The instant invention is further illustrated by the 5 following examples which are not intended to be in any way limitative.

Example I To a jar containing 64 ml. of water, 25 ml. of a solution of Glaubers salt (solution contained 20 mg. of Na SO .10H per ml. of solution) and 10 ml. of dilute formic acid (solution contained 12.5 mg. of formic acid Example II The procedure of Example I was repeated except that 55 ml. of water and 10 ml. of the solution of the 2,3: diphenylindole were used. The resulting fabric was markedly whiter than the blank.

Example III The procedure of Example I was repeated using a alcohol-acetone solution of 6-methyl-2,3 -diphenylindole with the same results.

Example IV The procedure of Example I was repeated using an alcohol-acetone solution of 5-methoxy-2,S-diphenylindole disclosed and claimed in Patent No. 2,845,437 with the same results.

Example V The procedure of Example I was repeated using an alcohol-acetone solution of 1,2-diphenyl-3H-benz(e)- indole with the same results.

Example VI The procedure of Example I was repeated using a acetone-dimethyl-formamide solution of 6-.acetamido-2,3-diphenylindole disclosed and claimed in copending application Ser. No. 592,746, filed on even date herewith, now abandoned, with the same results.

Example VII The procedure of Example I was repeated using an acetone-dimethyl-formamide solution of 5,5-bis-2,3-diphenylindole with the same results.

' Example VIII The procedure of Example II was repeated with 6- methyl-2,3-diphenylindole and the resulting fabric was markedly whiter in daylight.

Example IX The procedure of Example H was repeated with 5- methoxy-2,3-diphenylindole and the resulting fabric w markedly whiter in daylight.

Example X Theprocedure of Example 11- was repeated with"l,'2-'

diphenyl-3H-benz(e)indole and the resulting fabric was markedly whiter in daylight.

Example XI The procedure of Example II was repeated with 6- acetamido-2,3-dipheny1indole and the resulting fabric was markedly whiter in daylight.

Example XII The procedure of Example II was repeated with 5,5-

bis-2,3-diphenylindole and the resulting fabric was markedly whiter in daylight.

Example XIII The procedure of Example I was repeated with a 5 g. swatch of cellulose acetate being used in place of nylon. Noticeable whitening in daylight was observed.

Example XIV The procedure of Example )GII was repeated with 6- methyl-2,3-diphenylindole and'the resulting fabric was markedly whiter in daylight.

Example XV The procedure of Example XIII was repeated with 5- methoxy-2,3-diphenylindole and the resulting fabric was markedly whiter in daylight.

Example XVI The procedure of Example XIII was repeated with l,2-diphenyl-3H-benz(e)indole and the resulting fabric was markedly whiter in daylight.

Example XVII The procedure of Example XIII was repeated with 6- acetamido-2,3diphenylindole and the resulting fabric was markedly whiter in daylight.

Example XVIII The procedure of Example XIII was repeated with 5,5'-bis-2,3-diphenylindole and the resulting fabric was markedly whiter in daylight.

Example XIX The procedure of Example II was repeated with a 5 g. swatch of cellulose acetate being used in place of nylon. Noticeable whitening was observed.

Example XX The procedure of Example XIX was repeated with 6- methyl-2,3-diphenylindole and the resulting fabric was markedly whiter.

Example XXI The procedure of Example XIX was repeated with 5- meth0xy-2,3-diphenylindole and the resulting fabric was markedly whiter.

Example XXII The procedure of Example XIX Was repeatedwith 1,2-

diphenyl-3H-benz( e)indole and the resulting fabric was markedly whiter.

\ Example XXIII The procedure of Example )GX was repeated with 6- acetamido-Z,3-diphenylindole and the resulting fabric was markedly whiter.

7 Example XXIV The procedure of Example XIX was repeated with 5,5-bis-2,3-diphenylindole and the resulting fabric was markedly whiter.

Example XXV To 200 ml. of water containing 0.4 g. of soap at about 150 F. was added with agitation a ml. aliquot of an acetone-alcohol solution containing 125 mg. of 6-methyl- 2,3-diphenylindole per 50 ml. of solution. A 5 g. swatch of nylon was added and the system agitated at about 150' F. for 20 minutes. The cloth was rinsed well and agitated with soap solution containing no brightener at 150 F., again rinsed well and dried. Another swatch of cloth was treated similarly except that no brightener was added. Comparison of the two swatches showed that considerable whitening in daylight was imparted by the indole to the treated swatch.

8 Example XXVI The procedure of Example XXV was: repeated with a synthetic detergent (Tide) and cellulose acetate. Whitening in daylight was observed.

Example XX V lI The pnocedure of Example II was repeated with a 5 g. swatch of Dacron and with 6-acetarnido-2,3-diphenyl indole. A noticeable whitening in daylight resulted.

' Example XXVIII TABLE 1 Brlghtener Nylon Cellulose Concentra- Acetate tlonin Compound Batch (percent by wt. of R B R B cloth) Blank (untreated fabric) 49 3 43 2 i 0.5 28 60 2s 44 i 0. 05 43 26 41 13 CQHB CH O (36H;

H 1'0 CHQCONH Iona 88 CaHs CnHtt N CeHs 0.5 40 19 36 16 CtHl J2 R B=Brightness.

TABLE 2 [Table 2 dscribes brightness values of many other com- 1 pounds which were tested. The dyeings are at a concentration of .000005 mole of brightener per gram of cloth.]

Compound tested a R2 R4 [R=H, unless otherwise indicated] R! R4 R. R, R Nylon Cellulose Acetate I 13-14 30 35 --CaH 16 -C1- 11 11 0 CH3 NHCOCH3 16 25 Y --CH; 18 30 11 11 10 '1' 10-11 25 v 25 10 1O 40 --CH3 -CH3 15 15 -CHs CH5 15 15 I 1 -NCOCH3 10-11 10-11 Compound Tested 11 The signs mean that a slight fluorescence on the fabrics over untreated fabric could be observed but too little for any brightness reading, probabily less than 5.

It is to be understood that the foregoing detailed description is merely given by way of illustration and that many variations may be made therein without departing from the spirit of my invention.

Having described my invention, what I desire to secure by Letters Patent wherein R represents a member of the class consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, hydroxyalkyl, cyanoalkyl, arninoalkyl, and monoand di-alkyl substituted aminoalkyl; R R and R represent members of the class consisting of hydrogen, alkyl, alkoxy, hydroxy, carbalkoxy, cyano, amino, monoa-nd di-alkylamino, acylamido, aryl and aralkyl; R may additionally represent a second identical indole moiety connected by a connecting linkage which is a member of the class consisting of CH 0, S, S CO, CONH and a diphenyl linkage; x, y and z represent one of the integers 1-3; and wherein the ring designated a may be fused to a benzene ring and a pyrrole ring which is further substituted by diphenyl rings as defined by the rings designated b and c.

2. Process for achieving a brightening effect on white and colored fibers, filaments and fabrics of synthetic materials, which comprises applying to said fibers, filaments and fabrics an aqueous dispersion of from 0.05 to 0.5 based on the Weight of said fibers, filaments and fabrics, in a water-miscible organic solvent therefor, of 2,3-diphenylindole.

3. Process for achieving a brightening effect on white and colored fibers, filaments and fabrics of synthetic materials, which comprises applying to said fibers, filaments and fabrics an aqueous dispersion of from 0.05 to 0.5 based on the weight of said fibers, filaments and fabrics, in a water-miscible organic solvent therefor, of 2,3-diphenylindole substituted in at least one of the phenyl groups by a member of the class consisting of alkyl, alkoxy, hydroxy, carba-lkoxy, cyano, amino, monoand di-alkylamino, acylamido, aryl and aralkyl.

4. Process for achieving a brightening effect on white and colored fibers, filaments and fabrics of synthetic materials, which comprises applying to said fibers, filaments and fabrics, at a temperature of from to R, an aqueous dispersion of from 0.05 to 0.5 based on the weight of said fibers, filaments and fabrics, in a water-miscible organic solvent therefor, of 2,3-diphenylindole.

5. Process for achieving a brightening effect on white and colored fibers, filaments and fabrics of synthetic materials, which comprises applying to said fibers, filaments and fabrics, at a temperature of from 150 to 180 R, an aqueous dispersion of from 0.05 to 0.5 based on the weight of said fibers, filaments and fabrics, in a watermiscible organic solvent therefor, of 2,3-diphenylindole substituted in at least one of the phenyl groups by a member of-the class consisting of alkyl, alkoxy, hydroxy, carbalkoxy, cyano, amino, monoand di-alkylamino, acylamido, aryl and aralkyl.

6. Process for achieving a brightening eifect on white and colored fibers, filaments and fabrics of synthetic materials selected from the group consisting of nylon and cellulose acetate, which comprises applying to said fibers, filaments and fabrics, at a temperature of from 150 to 180 R, an aqueous dispersion of from 0.05 to 0.5%, based on the weight of said fibers, filaments and fabrics, in a water-miscible organic solvent therefor, of 2,3-diphenyl-indole. V

7. Process for achieving a brightening effect on white and colored fibers, filaments and fabrics of synthetic materials selected from the group consisting of nylon and cellulose acetate, which comprises applying to said fibers, filaments and fabrics, at a temperature of from 150 to 180 R, an aqueous dispersion of from 0.05 to 0.5%, based on the weight of said fibers, filaments and fabrics, in a water-miscible organic solvent therefor, of 2,3-diphenylindole substituted in at least one of the phenyl groups by a member of the class consisting of alkyl, alkoxy, hydroxy, carbalkoxy, cyano, amino, monoand di-alkylamino, acyllarnido, aryl and aralkyl.

References Cited in the file of this patent UNITED STATES PATENTS 1,780,058 Ballauf Oct. 28, 1930 2,057,948 Herdieckerhoff et a1 Oct. 20, 1936 2,460,745 Grimmel et a1 Feb. 1, 1949 2,510,428 Standen June 6, 1950 2,510,432 Stewart June 6, 1950 2,713,046 Williams'et all. July 12, 1955 FOREIGN PATENTS 112,132 Austria Jan. 25, 1929 533,471 Germany Sept. 12, 19351 OTHER REFERENCES Chemical Abstracts, vol. 33 (1939), page 4127, article by Fialkovsk-aya. 

1. PROCESS FOR ACHIEVING A BRIGHTENING EFFECT ON WHITE AND COLORED FIBERS, FILAMENTS AND FABRICS OF SYNTHETIC MATERIALS, WHICH COMPRISES APPLYING TO SAID FIBERS, FILAMENTS AND FABRICS AN AQUEOUS DISPERSION OF FROM 0.05 TO 0.5%, BASED ON THE WEIGHT OF SAID FIBERS, FILAMENTS AND FABRICS, IN A WATER-MISCIBLE ORGANIC SOLVENT THEREFOR, OF A DIPHENYLINDOLE OF THE FORMULA 